Lanthanide Identity Governs Guest-Induced Dimerization in LnIII[15-MC N(L-pheHA)-5])3+ Metallacrowns

Series of lanthanide-containing metallic coordination complexes are frequently presented as structurally analogous, due to the similar chemical and coordinative properties of the lanthanides. In the case of chiral (Ln^III[15-MC _N(L-pheHA)-5])³⁺ metallacrowns (MCs), which are well established supramolecular hosts, the formation of dimers templated by a dicarboxylate guest (muconate) in solution of neutral pH is herein shown to have a unique dependence on the identity of the MC's central lanthanide. Calorimetric data and nuclear magnetic resonance diffusion studies demonstrate that MCs containing larger or smaller lanthanides as the central metal only form monomeric host-guest complexes whereas analogues with intermediate lanthanides (for example, Eu, Gd, Dy) participate in formation of dimeric host-guest-host compartments. The driving force for the dimerization event across the series is thought to be a competition between formation of highly stable MCs (larger lanthanides) and optimally linked bridging guests (smaller lanthanides).     

J-Stabilization of singlet states in the solution NMR of multiple-spin systems

Long-lived singlet states have been observed in the solution NMR of spin systems containing more than two coupled spins, despite the fact that the singlet state is expected to be quenched by small long-range J-couplings. We show that the stability of localized singlet states may be explained by taking into account the intra-pair J-coupling between the two spins which participate in the singlet state. The relatively strong intra-pair J-coupling protects the singlet state against quenching by weaker out-of-pair J-couplings.     

The role of copper(II) and zinc(II) in the degradation of human and murine IAPP by insulin‐degrading enzyme

Amylin or islet amyloid polypeptide (IAPP) is a 37‐residue peptide hormone secreted from the pancreatic islets into the blood circulation and is cleared by peptidases in the kidney. IAPP aggregates are strongly associated with β‐cell degeneration in type 2 diabetes, as demonstrated by the fact that more than 95% of patients exhibit IAPP amyloid upon autopsy. Recently, it has been reported that metal ions such as copper(II) and zinc(II) are implicated in the aggregation of IAPP as well as able to modulate the proteolytic activity of IAPP degrading enzymes. For this reason, in this work, the role of the latter metal ions in the degradation of IAPP by insulin‐degrading enzyme (IDE) has been investigated by a chromatographic and mass spectrometric combined method. The latter experimental approach allowed not only to assess the overall metal ion inhibition of the human and murine IAPP degradation by IDE but also to have information on copper‐ and zinc‐induced changes in IAPP aggregation. In addition, IDE cleavage site preferences in the presence of metal ions are rationalized as metal ion‐induced changes in substrate accessibility. Copyright © 2014 John Wiley & Sons, Ltd.     

Effects of Cations on HPTS Fluorescence and Quantification of Free Gadolinium Ions in Solution; Assessment of Intracellular Release of Gd3+ from Gd-Based MRI Contrast Agents

8-Hydroxypyrene-1,3,6-trisulfonate (HPTS) is a small, hydrophilic fluorescent molecule. Since the pKa of the hydroxyl group is close to neutrality and quickly responds to pH changes, it is widely used as a pH-reporter in cell biology for measurements of intracellular pH. HPTS fluorescence (both excitation and emission spectra) at variable pH was measured in pure water in the presence of NaCl solution or in the presence of different buffers (PBS or hepes in the presence or not of NaCl) and in a solution containing BSA. pKa values have been obtained from the sigmoidal curves. Herein, we investigated the effect of mono-, di-, and trivalent cations (Na⁺, Ca²⁺, La³⁺, Gd³⁺) on fluorescence changes and proposed its use for the quantification of trivalent cations (e.g., gadolinium ions) present in solution as acqua-ions. Starting from the linear regression, the LoD value of 6.32 µM for the Gd³⁺ detection was calculated. The effects on the emission were also analyzed in the presence of a combination of Gd³⁺ at two different concentrations and the previously indicated mono and di-valent ions. The study demonstrated the feasibility of a qualitative method to investigate the intracellular Gd³⁺ release upon the administration of Gd-based contrast agents in murine macrophages.     

Raman polarization analysis of highly crystalline polyethylene fiber

The complex orientation dependence in space of Raman active vibrations in the orthorhombic structure of polyethylene (PE) is discussed in terms of Raman tensor elements as intrinsic physical parameters of the lattice. Building upon the symmetry assignment of these vibrational modes, we systematically studied, from both theoretical and experimental viewpoints, the changes of polarized intensity for the A_g and the B_2g + B_3g vibrational modes with respect to PE molecular orientation. After explicitly expanding the Raman selection rules associated with the A_g and the B_2g + B_3g modes, introducing them into general expressions of the orientation distribution function, and validating them by means of a least‐square fitting procedure on experimental data, we compare here two mesostructural models for a highly crystallized and self‐aligned PE fiber structure. Stereological arguments are shown concerning the arrangement of orthorhombic fibrils in such a sample that unfold the correct values of five independent Raman tensor elements for orthorhombic PE. Copyright © 2010 John Wiley & Sons, Ltd.     

Vibrazioni e pressioni critiche delle piastre anulari soggette a pressione radiale

Sommario Viene studiato il problema delle vibrazioni trasversali delle piastre anulari soggette a pressioni radiali sui due bordi e viene stabilita una condizione sufficiente di esistenza di autovalori reali del parametro da cui dipendono le autofrequenze. Si collega il problema delle vibrazioni a quello delle pressioni critiche caratterizzando l'andamento delle curve di autofrequenza. Vengono fatte osservazioni intorno al comportamento dell'energia totale e al lavoro della sollecitazione radiale in corrispondenza ai termini quadratici delle caratteristiche di deformazione. Lavoro eseguito nell'Istituto Nazionale per le Applicazioni del Calcolo, Roma.     

A novel statistical linearization solution for randomly excited coupled bending-torsional beams resting on non-linear supports

A novel statistical linearization technique is developed for computing stationary response statistics of randomly excited coupled bending-torsional beams resting on non-linear elastic supports. The key point of the proposed technique consists in representing the non-linear coupled response in terms of constrained linear modes. The resulting set of non-linear equations governing the modal amplitudes is then replaced by an equivalent linear one via a classical statistical error minimization procedure, which provides algebraic non-linear equations for the second-order statistics of the beam response, readily solved by a simple iterative scheme. Data from Monte Carlo simulations, generated by a pertinent boundary integral method in conjunction with a Newmark numerical integration scheme, are used as benchmark solutions to check accuracy and reliability of the proposed statistical linearization technique.

     

A Reader’s Comment on: “Hysteresis Model of Unconscious-Conscious Interconnection: Exploring Dynamics on m-Adic Trees”

p-Adic Numbers, Ultrametric Analysis and Applications - This comment is aimed to point out that the recent work due to H. Kim, J-Y. Moon, G. A. Mashour and U. Lee ([22]), in which the clinical and...